CN108299669A - Hydrophobic porous starch and its purposes in adsorbing oils - Google Patents
Hydrophobic porous starch and its purposes in adsorbing oils Download PDFInfo
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- CN108299669A CN108299669A CN201810080020.2A CN201810080020A CN108299669A CN 108299669 A CN108299669 A CN 108299669A CN 201810080020 A CN201810080020 A CN 201810080020A CN 108299669 A CN108299669 A CN 108299669A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/06—Esters
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Abstract
The present invention relates to environment-friendly materials field more particularly to hydrophobic porous starch and its purposes in adsorbing oils.In conjunction with enzymolysis pretreatment, octenyl succinic acid anhydride（OSA）Hydrophobically modified and Al3+It is crosslinked and composite modified prepares hydrophobic porous starch.Alpha amylase cooperates with processing with glucase, makes the hole of starch particle surface formation from outward appearance to inner essence, forms porous-starch.The oil absorbency of hydrophobic porous starch increases with the increase of percent hydrolysis, reaches as high as 52.3%.Adsorption rate to corn oil, machine oil, diesel oil is respectively 80.4%, 52.3% and 41.9%.Water absorption rate only has 6% or so in grease system, shows good oil-water selectivity energy, and Oil keeping is good.
Description
Technical field
The present invention relates to environmentally friendly material sphere more particularly to hydrophobic porous starch and its purposes in adsorbing oils.
Background technology
With the fast development of global economy, the demand of various countries' oil is in the trend for aggravating to increase.However, being opened in oil
Adopt, process and transportational process occur leakage accident happen occasionally.Oil pollution generally have duration is strong, range of scatter is wide,
The features such as disposition is difficult, harm is big, it has also become current important one of environmental pollution accident.The discharge of greasy dirt polluted underground water simultaneously
And surface water, make ecological environment by fatal destruction, bio-diversity falls sharply, and is constituted sternly to the ecosystem and human health
It threatens again, the resident near polluted water region is also made to deeply hurt.
Currently, being mainly the following method processing marine oil spill pollution：First, using hydrocarbon degradation bacteria to ocean
Oil spilling is degraded；Second is that situ combustion method；The third method is such as to collect finish by adding chemical treatments, fuel thickener, divide
Powder etc.；Fourth, physical method, is surrounded the oil spilling of ocean surface using the oil fence, then oil absorption material is recycled to receive oil spilling
Collection gets up.Oil absorption material is a kind of very effective marine oil spill processing method, has the spies such as efficient, economy, oil product easily recycling
Point is widely used in marine oil spill contamination accident emergency processing.So the research and development of oil absorption material are concerned in recent years,
The oil absorption material that research and development are efficient, clean, recycle realizes that water-oil separating becomes recent research hot spot.
Although the oil treatment process that overflows has very much, physisorphtion is common effective processing method, it can be with
The secondary pollution to environment is avoided, is the cost-effective method for handling oil spilling.Physisorphtion is carried out using oil absorption material, it
The network structure formed using the capillarity of oil absorption material surface, gap and cavity or intermolecular physical condensation power
Oil or grease are collected, converts the oil product of liquid to semi-solid phase, then effectively removes sea by removing the approach of oil absorption material
The greasy dirt in face.
By the difference of constituent material type, oil absorption material can be divided into following a few classes：It is natural inorganic oil absorption material, natural organic
Oil absorption material and chemical synthesis class oil absorption material.It is the common active charcoal of natural inorganic oil absorption material, zeolite, perlite, viscous
Soil, vermiculite, Silica hydrogel and graphite, this kind of material is generally in granular form or with loose porous structure, cheap, material is easy
, speed of oil absorption is fast, but the shortcomings of most of material there are oil-water selectivities poor, saturation low oil absorption capacity, regeneration difficulty.Naturally
Organic oil absorption material includes straw, rice husk, rush, straw, mestha, bark etc., this kind of material also have it is cheap, be easy to get and
The advantages that biodegradable, but that there is also oil-water selectivities is poor, saturation oil absorption is relatively low, suspension is poor lacks
Point.Common chemical synthesis class oil absorption material has polypropylene fibre, polyurethane foam and high oil-absorbing resin.Chemical synthesis class
The lipophilic-hydrophobic property of oil absorption material is good, and oil absorption protrudes, but biological degradability is poor.
One process to develop from tradition to high-performance type of the development experience of oil absorption material.Initial people using sponge,
The porous materials such as clay carry out oil suction, but result is unsatisfactory, and this oil absorption material has the shortcomings that apparent：(1) oil mass is not
Greatly, oil suction multiplying power (mass ratio) is small；(2) water selective is not high, often also absorbs water while oil suction；(3) Oil keeping is poor after oil, slightly
One pressurization will oil leak again.The presence of these disadvantages makes their application be restricted.Later, people were by surface-active
Agent surface changes sexual enlightenment, and oil absorption material is done with oil sucting pad, if polypropylene fibre asphalt felt is using allyl resin as raw material, using the company of spinning
One step networking of method, then prepared by through needle felting, oil sucting pad itself is oleophilic substance or is oleophilic substance after modified, therefore
The oil absorbency and oil-water selectivity of oil sucting pad all increase, but but cannot still be solved the problem of oil leak again under plus-pressure
Certainly.Recent years, researchers are inspired by the certain theoretical of high hydroscopic resin, make oil absorption material to high oil-absorbing resin
Development.The polymer that more high oil-absorbing resin is often low cross-linking is studied at present, it is using lipophile monomer as base unit, warp
The oil of appropriately crosslinked composition network structure, absorption is stored in Van der Waals force in this network.This oil absorption material oil suction multiplying power
Height, oil-water selectivity are good, and protect oil performance greatly improves, and is not easy oil leak again, is a kind of high performance new material.It is domestic right
Than later, only several colleges and universities and research institute are carrying out this work, are ground still in laboratory for the research starting of this respect
Study carefully the stage, is badly in need of developing better polymeric material, the oil absorbency of oil-absorbing resin is improved to realize using new polymerization technique
It is industrialized.
Environmentally friendly oil absorption material is the Main way of current external oil absorption material development, is ensureing oil absorbency satisfaction
When actual requirement, start the recycling for increasingly focusing on material and biodegradation character.
The research of the starch absorption carrier obtained in conjunction with enzymatic treatment, hydrophobically modified and metal ion crosslinked is at present also in sky
In vain, the pertinent literature of oily pollution water process is not used it for yet.
Invention content
The purpose of invention：In order to provide a kind of better hydrophobic porous starch of effect and its use in adsorbing oils
On the way, specific purposes are shown in multiple substantial technological effects of specific implementation part.
In order to reach purpose as above, the present invention adopts the following technical scheme that：
Following scheme includes multiple independent alternatives：
Hydrophobic porous starch, which is characterized in that be prepared using following steps.
(1) preparation of porous-starch
It weighs cornstarch to be scattered in the citrate-phosphate disodium hydrogen buffer solution that pH is 5, is made into 23% (w/w's)
Complex enzyme (alpha-amylase and glucase by volume 1 is added in starch milk solution:3 mixing) after in 50 DEG C enzymolysis, reaction
After the completion, so that enzyme is inactivated to 3 reaction 15min with 5% salt acid for adjusting pH, finally use the hydrochloric acid in 3%NaOH and in solution；Instead
After the completion of answering, vacuum filtration, starch is washed with deionized 2-3 times and is placed in air dry oven at 45 DEG C dry 48h, crushes
80 mesh sieve is crossed afterwards to get to porous enzymatic starch
(2) octenyl succinic acid anhydride (OSA) esterification of porous-starch
The enzymatic starch breast for allocating a concentration of 35% (w/w), is placed in 35 DEG C of water-baths, is stirred continuously, adjust starch milk
PH, make it in the range of 8.0-8.5,5% OSA (w/w accounts for starch on dry basis quality), reaction process be added dropwise in 1h
It is middle with 3% NaOH solution control system pH；It is after reaction neutral with 5% salt acid for adjusting pH；Multiple alcohol is washed, water
It washes, filter and dries sample.
(3) it is esterified the Al of enzymatic starch3+Crosslinking
It takes the starch sample of above-mentioned esterification enzymolysis to be configured to the starch milk of a concentration of 35% (w/w), adjusts reaction system
PH is 4, and quantitative Al is added3+, pH is maintained with 3% NaOH in reaction process, after reaction, is repeatedly washed, is filtered postposition
Drying for 24 hours, obtains composite modified hydrophobic porous starch in 45 DEG C of baking oven.The further technical solution of the present invention is, also wraps
Preferred step is carried out containing the hydrophobic porous starch, the carry out is preferred, refers to being carried out to Hydrophobic Modified Starch particle
Levels starch is obtained after separation, the oil absorbency of upper layer starch lower layer starch is more preferable, collects upper layer starch.
The further technical solution of the present invention is that the amount that the OSA is added is 5% (w/w accounts for starch on dry basis quality).
OSA and cornstarch it is one of arbitrary or a combination thereof preparing hydrophobic porous starch or hydrophobic porous oil suction object
Purposes in matter.
The purposes of hydrophobic porous starch produced as described above in adsorbing and keeping fuel oil and/or edible oil.
Hydrophobic porous starch produced as described above can adsorb greasy dirt of the cleaning substance to tank bottom.
The purposes of hydrophobic porous starch produced as described above in preparing the environmentally friendly substance for administering oily waste water treatment.
The purposes of hydrophobic porous starch produced as described above in the emergency management and rescue that oil reveals in water body.
Open oil-contaminated water processing method, which is characterized in that it comprises the following steps,
Containing region prevents the greasy dirt on the water surface from continuing to spread；The mode contained is to use containment structure, containment structure packet
Plate is contained in buoyant foam containing lower section, lower section buoyant foam top comprising top, and plate is contained in top and buoyant foam composition in lower section is enclosed
Bridging structure, containment structure, which surrounds, contains circle, and it is to contain region that it is internal, which to contain circle,；
The substance described in this patent is added；Stirring layering；Intercept upper layer substance；Upper layer substance is dried, combustion is used as
Expect spare.
The processing method of closed oily wastewater：Sewage is collected, is conducted into process container；The process container
Including oily wastewater import, it is provided with adding mouth on oily wastewater import inside, the substance described in this patent can be added in adding mouth,
The substance that oily wastewater can impact this patent addition so that it is impacted in container；Layering；Upper layer substance is intercepted, under separation
Layer substance；Lower section receiver is the double-deck platy structure, and hole is respectively contained on the double-deck platy structure, by changing the double-deck platy structure
Hole registration can adjust lower section receiver mesh, when with lift part pull lower section receiver move downward when
It waits, the mesh of lower section receiver is opened, and the substance of oily wastewater and this patent addition is then added；After sedimentation, lower section is held
The mesh for connecing object is relatively closed, can opposite barrier by the floating fraction of top；Upper layer substance is dried, it is standby to be used as fuel
With.
Using the present invention of technical solution as above, have the advantages that compared with the existing technology：This patent combines enzymolysis
Pretreatment, octenyl succinic acid anhydride (OSA) hydrophobically modified and Al3+It is crosslinked and composite modified prepares hydrophobic porous starch.It has inquired into and has added
Influence of the enzyme amount to hydrophobic porous starch structure and physicochemical property, and oil absorbency is inquired into.Research is found：Alpha-amylase
Processing is cooperateed with glucase, is made the hole of starch particle surface formation from outward appearance to inner essence, is formed porous-starch.Identical
Under OSA additive amounts, with the increase of enzyme concentration, the degree of substitution of hydrophobic porous starch reduces.Laser confocal microscope shows ester
Octenyl succinic acid groups (OS) are distributed in entire particle after change processing, and with the raising of enzyme hydrolysis rate, OS groups are more
Ground is distributed in the inside of hydrophobic porous starch granules.The oil absorbency of hydrophobic porous starch increases with the increase of percent hydrolysis, highest
Up to 52.3%.Adsorption rate to corn oil, machine oil, diesel oil is respectively 80.4%, 52.3% and 41.9%.In grease system
Water absorption rate only has 6% or so, shows good oil-water selectivity energy, and Oil keeping is good.
Description of the drawings
In order to further illustrate the present invention, it is further illustrated below in conjunction with the accompanying drawings：
Fig. 1 is the schematic diagram that machine oil is bubbled through the water column；
Schematic diagram when Fig. 2 is initially added for Hydrophobic Modified Starch；
Fig. 3 is the schematic diagram stirred in oil-absorbing process；
Fig. 4 is the schematic diagram after the completion of oil suction；
Fig. 5 is the curve graph of the protect oil performance of the water delivery porous-starch of the present invention；
Fig. 6 is the structural schematic diagram of the stop portions of open oil-contaminated water processing method；
Fig. 7 is the enclosing region overlooking structure diagram of open oil-contaminated water processing method；
Fig. 8 is the processing device structure diagram of closed oily wastewater；
Fig. 9 is one of the realization structure of double-layer leaching net；
1. lower section buoyant foam；2. 3. water surface of plate is contained in top；4. containing circle；5. containing region；6. oily wastewater import；
7. adding mouth；8. avris adsorption structure；9. lower section receiver；10. lifting part；11. lower exit port.
Specific implementation mode
With reference to the accompanying drawings and detailed description, the present invention is furture elucidated, but the scope of protection of present invention is simultaneously
It is not limited solely to the range of example statement.
Hydrophobic porous starch, which is characterized in that be prepared using following steps.
(1) preparation of porous-starch
It weighs cornstarch to be scattered in the citrate-phosphate disodium hydrogen buffer solution that pH is 5, is made into 23% (quality point
Number) starch milk solution, complex enzyme (alpha-amylase and glucase by volume 1 is added:3 mixing) after in 50 DEG C of enzymes
Solution after the completion of reaction, makes enzyme inactivate, finally uses in 3%NaOH and in solution with 5% salt acid for adjusting pH to 3 reaction 15min
Hydrochloric acid；After the completion of reaction, vacuum filtration, starch is washed with deionized 2-3 times and is placed in air dry oven drying at 45 DEG C
48h smashes it through 80 mesh sieve to get to porous enzymatic starch
(2) octenyl succinic acid anhydride (OSA) esterification of porous-starch
The enzymatic starch breast for allocating a concentration of 35% (w/w), is placed in 35 DEG C of water-baths, is stirred continuously, adjust starch milk
PH, make it in the range of 8.0-8.5,5% OSA (w/w accounts for starch on dry basis quality), reaction process be added dropwise in 1h
It is middle with 3% NaOH solution control system pH；It is after reaction neutral with 5% salt acid for adjusting pH；Multiple alcohol is washed, water
It washes, filter and dries sample.
(3) it is esterified the Al of enzymatic starch3+Crosslinking
It takes the starch sample of above-mentioned esterification enzymolysis to be configured to the starch milk of a concentration of 35% (w/w), adjusts reaction system
PH is 4, and quantitative Al is added3+, pH is maintained with 3% NaOH in reaction process, after reaction, is repeatedly washed, is filtered postposition
Drying for 24 hours, obtains composite modified hydrophobic porous starch in 40 DEG C of baking oven.The skill for the essence that the technical solution at this place is played
Art effect and its realization process are as follows：
In conjunction with enzymolysis pretreatment, OSA hydrophobically modifieds, Al3+Three kinds of method of modifying of crosslinking handle native cornstarch, make
Standby Hydrophobic Modified Starch.A series of indexs such as oil absorbency of the Hydrophobic Modified Starch of preparation are determined, different enzymolysis items have been investigated
Influence of the part to hydrophobic porous starch physicochemical property, and observe the oil-absorbing process and mode of appearance of hydrophobic porous starch.Experiment
The result shows that：
(1) influence of enzyme concentration and enzymolysis time to percent hydrolysis can be divided into two stages：First stage hydrolysis rate increases
It is exceedingly fast greatly, second stage, which is increased speed, to be obviously reduced.Enzyme hydrolysis destroys the surface texture of starch granules, and hydrophobic porous is caused to form sediment
The degree of substitution and activation index of powder sample all decrease.
(2) percent hydrolysis is bigger to be shown to the measurement of oil absorbency, oil absorbency is higher；The esterification of OSA and Al simultaneously3+Crosslinking
Effect further improve adsorption capacity of the hydrophobic porous starch to machine oil, when OSA additive amounts be 5%, percent hydrolysis 27.8%
When, oil absorbency is up to 52.3%, and 22.9% is improved compared with native cornstarch.
(3) without enzymolysis when, largely paste is on the surface of hydrophobic porous starch granules for machine oil, with the increase of percent hydrolysis,
Part machine oil, which can penetrate into inside starch granules, to be adsorbed in hole, initially dry to form sediment in powdered hydrophobic porous after the completion of oil suction
Powder becomes fluffy sticky state.
The surface topography of Hydrophobic Modified Starch, the OS groups distribution feelings of architectural characteristic and different percent hydrolysis Hydrophobic Modified Starch
Condition conclusion is as follows：
(1) starch granules is after enzymolysis pre-processes, it may appear that and it is a degree of broken, but still there is polarized light property,
However as the increase of Degree of Enzymatic Hydrolysis, the birefringence intensity of Hydrophobic Modified Starch Birefringence gradually weakens, the nothing of crystalline texture
Sequenceization increases.
(2) to carrying out infrared spectrum detection through digesting pretreated OS starch esters, it was found that C=O (1724cm-1) and-
COO-(1573cm-1) two new absorption peaks, this is the typical IR characteristic absorption peak of OS starch esters, and with the increasing of percent hydrolysis
Greatly, two characteristic absorption peaks become more flat, it was demonstrated that the degree of substitution (DS) of hydrophobic porous starch gradually drops after enzymolysis pretreatment
It is low, thus lead to crosslinked Al3+Content is gradually reduced, and 0.152 is reduced to by 0.234.
(3) combine laser co-focusing and x-ray photoelectron spectroscopy investigation OS groups in the distribution situation of starch granules, as a result
It confirms：When without enzymolysis, OS groups are distributed in entire particle, most of in the periphery of particle；OSA drops can ooze after enzymolysis
It penetrates into and esterification occurs into starch granules kernel area, OS groups is made more to be distributed in the interior of hydrophobic porous starch granules
Portion, and as the raising of percent hydrolysis, the surface degree of substitution of starch granules continuously decrease, internal degree of substitution is gradually increased.
Starch can be cornstarch, rice starch either tapioca.
Absorbent properties of the hydrophobic porous starch to different oil products
It is hydrophobic porous starch to the absorbent properties of different oil, suction of the hydrophobic porous starch to corn oil, machine oil and diesel oil
Attached ability is respectively 80.4%, 52.3% and 41.9%, maximum to the adsorption capacity of corn oil, most to the adsorption capacity of diesel oil
Small, this may be related with the molecular weight of these three oil and molecular chain length.
Hydrophobic Modified Starch mainly using the hole volume inside faint Van der Waals force oil suction and starch granules come
Oil suction, the difference to different oil product oil absorptions are mainly caused by the density and viscosity due to oil product itself.Corn oil and machine
The density and viscosity of oil is larger, and the oil product of quality bigger can be stored in certain space, and the density and viscosity of diesel oil is minimum, and one
The quality for determining to be stored in space is also minimum；There is absorption gender gap of the hydrophobic Long carbon chain OS groups to these three oil simultaneously
Less, so Hydrophobic Modified Starch is best to the adsorptivity of corn oil.
Oil absorbency of the hydrophobic porous starch under dynamic and static conditions is compared, finds hydrophobic porous starch in dynamic condition
Under oil absorbency be more than static conditions under oil absorbency.This is because in a static condition, the viscosity resistance between starch granules
The contact between oil droplet and starch granules is hindered, has made it be difficult to penetrate into inside hydrophobic porous starch granules, therefore in static conditions
Its lower oil absorbency is relatively low；On the contrary in a dynamic condition, the effect of magnetic agitation enables oil droplet to penetrate sufficiently into starch granules
Inner void, and more oil can be also adsorbed between the starch granules of dispersity, each contribute to the suction of hydrophobic porous starch
The raising of oil cut rate.
During oil spilling processing at sea, the recovery processing of oil is carried out usually after sucking oil, but is being transported
When material after oil suction, the phenomenon that not strong oil absorption material of oil-retaining will appear secondary oil spilling.Protect oil performance is evaluation
One important performance indicator of oil absorption material.The good oil absorption material of protect oil performance is not in oil under small external force
Overflow, and between duct is bigger and fiber the incomplete oil absorption material of skeleton under mobile or small external force, inhale
The oil of receipts can overflow again.
In order to evaluate the protect oil performance of prepared Hydrophobic Modified Starch, to the hydrophobic porous starch after saturation oil suction carry out from
The heart, and its mass ratio is measured, the results are shown in Figure 5, and as seen from the figure, with the increase of centrifugal force, guarantor's oil cut rate of starch has
It is reduced, but reduces amplitude very little, substantially remain in 90% or more.Thus illustrate prepared hydrophobic porous starch oil suction material
The protect oil performance of material is fine, the oil spill of absorption can't be enabled to go out under small centrifugal force, so treated transported in oil spilling
Cheng Zhong usually will not enable the oil stream of absorption go out, can be to avoid the danger of secondary pollution.Why hydrophobic porous starch has well
Protect oil performance is since its structure influences, and hydrophobic porous starch is formed on surface later because the duct that enzymolysis is formed can absorb oil
One layer of oil film to prevent the spilling of oil, and hydrophobic porous starch carries out crosslinking with good mechanical performance after enzymolysis and
Another reason for being unlikely to deform, and enabling protect oil performance that it has had.
Protect oil performance test is carried out to prepared hydrophobic porous starch oil absorption material, is found under the conditions of different centrifugal force
It protects oil cut rate and substantially remains in 90% or more, it is existing that small centrifugal force can't enable the hydrophobic porous starch for being saturated with oil that oil leak occurs
As, it was demonstrated that prepared oil absorption material has good protect oil performance.
Preferred step also is carried out comprising the hydrophobic porous starch, the carry out is preferred, refers to hydrophobically modified
Starch granules obtains levels starch after being detached, the oil absorbency of upper layer starch lower layer starch is more preferable, collects upper layer and forms sediment
Powder.
It can be seen that the oil absorbency of upper layer starch is continuously increased with the rising of percent hydrolysis after separation, and upper layer starch
Oil absorbency is significantly greater than the oil absorbency of former Hydrophobic Modified Starch and lower layer's starch.It includes mainly two that investigating, which influences the factor of oil absorbency,
A aspect, when the porous structure of starch granules, but the hydrophobic grouping distribution situation of starch particle surface and inside.By preceding
The analysis of face chapters and sections learns that the percent hydrolysis of levels starch is identical, and the porous structure of formation is similar, therefore influences the original of oil absorbency
It is different in the distribution situation of starch granules because essentially consisting in hydrophobic grouping.And by the measurement result mating surface element of degree of substitution
Distribution situation is it is found that the degree of substitution of upper layer starch is more than lower layer's starch, and OS hydrophobic groupings are more distributed in upper layer starch
The surface of grain, instead in the more of the inside of lower layer's starch granules distribution, this may be because of levels starch granules and original
The porous structure that Hydrophobic Modified Starch is formed is not much different, and oil can substantially fill entire hole, thus inside starch granules
Hydrophobic grouping to the contribution of its oil absorbency almost without therefore the difference of oil absorbency essentially consists in the hydrophobic group of surface distribution
Group, and the distribution of the OS hydrophobic groupings of upper layer starch is more conducive to Al more than former Hydrophobic Modified Starch and lower layer's starch3+Bridge formation hand over
Connection acts on, and has good effect to the shielding of starch hydroxyl, is conducive to improve the oil absorbency of starch.Therefore upper layer starch is shown
Oil absorbency be better than former Hydrophobic Modified Starch and lower layer's starch.
After modified starch particle is dispersed in water the separation for carrying out levels starch, a series of properties is carried out to it
It measures, the results showed that：
(1) a little higher than former hydrophobic porous starch of the degree of substitution of upper layer starch, and the degree of substitution of lower layer's starch is relatively low, only
0.005 or so, this matches with the results of IR of hydrophobic porous starch, it was demonstrated that octenyl succinic acid anhydride is in starch
The reaction of grain is uneven, and partial starch particle will not react with OSA；And starch granules through enzymolysis pre-process after,
OS groups can go deep into being reacted inside starch granules.
(2) OS groups are largely distributed in the surface of upper layer starch granules, and OS groups are in lower layer's starch in contrast
The inside distribution of particle is more so that the Al of upper layer starch granules3+Content is higher than lower layer's starch.
(3) hydrophobic porous starch granules OS group degree of substitution is the key factor for influencing starch oil absorbency, upper layer starch
The oil absorbency of lower layer starch is more preferable, main reason is that OS groups are in the case where the distribution situation of upper layer starch particle surface is better than
Layer starch.
The amount that the OSA is added is 5% (w/w accounts for starch on dry basis quality).
OSA and cornstarch it is one of arbitrary or a combination thereof preparing hydrophobic porous starch or hydrophobic porous oil suction object
Purposes in matter.
The purposes of hydrophobic porous starch produced as described above in adsorbing and keeping fuel oil and/or edible oil.
A kind of substance of grease factory cleaning oil tank, which is characterized in that tank bottom is carried out using the cleaning substance
Cleaning, the cleaning substance are：
Hydrophobic porous starch, which is characterized in that be prepared using following steps.
(1) preparation of porous-starch
It weighs cornstarch to be scattered in the citrate-phosphate disodium hydrogen buffer solution that pH is 5, is made into 23% (quality point
Number) starch milk solution, complex enzyme (alpha-amylase and glucase by volume 1 is added:3 mixing) after in 50 DEG C of enzymes
Solution after the completion of reaction, makes enzyme inactivate, finally uses in 3%NaOH and in solution with 5% salt acid for adjusting pH to 3 reaction 15min
Hydrochloric acid；After the completion of reaction, vacuum filtration, starch is washed with deionized 2-3 times and is placed in air dry oven drying at 45 DEG C
48h smashes it through 80 mesh sieve to get to porous enzymatic starch
(2) octenyl succinic acid anhydride (OSA) esterification of porous-starch
The enzymatic starch breast for allocating a concentration of 35% (w/w), is placed in 35 DEG C of water-baths, is stirred continuously, adjust starch milk
PH, make it in the range of 8.0-8.5,5% OSA (w/w accounts for starch on dry basis quality), reaction process be added dropwise in 1h
It is middle with 3% NaOH solution control system pH；It is after reaction neutral with 5% salt acid for adjusting pH；Multiple alcohol is washed, water
It washes, filter and dries sample.
(3) it is esterified the Al of enzymatic starch3+Crosslinking
It takes the starch sample of above-mentioned esterification enzymolysis to be configured to the starch milk of a concentration of 35% (w/w), adjusts reaction system
PH is 4, and quantitative Al is added3+, pH is maintained with 3% NaOH in reaction process, after reaction, is repeatedly washed, is filtered postposition
Drying for 24 hours, obtains composite modified hydrophobic porous starch in 45 DEG C of baking oven.
The corresponding prior art defect of technology at this place is：Especially edible oil and fat factory of present grease factory, cleaning oil tank is all
A large amount of clean rag oil suction is needed, waste of material situation is very serious, and human cost is higher.
A kind of high heat solid fuel, which is characterized in that it is hydrophobic porous starch adsorption chemical industry oil produced as described above
It is prepared after fat.
Using this structure, the waste grease etc. in liquid can be made full use of, also to be used as fuel.
The purposes of hydrophobic porous starch produced as described above in preparing the environmentally friendly substance for administering oily waste water treatment.
The purposes of hydrophobic porous starch produced as described above in the emergency management and rescue that oil reveals in water body.This place is appreciated that
For ocean oil leak etc..
Adsorb the hydrophobic porous starch needed for every gram of machine oil
Hydrophobic porous starch sample is added in the mixture of machine oil and water and measures its oil absorbency, specific method is, accurately
100g deionized waters are weighed, and the machine oil of 2g is added, oil water mixture is formed, measures its quality m2, it is gradually added into hydrophobic porous
Starch sample, and be stirred continuously, until when the starch sample being added just adsorbs whole machine oil, measure quality m at this time1。
Adsorb minimum content of starch (g/g)=(m needed for every gram of machine oil1-m2)/m2× 100%
Wherein, m0Represent the quality (g) of machine oil, m1Represent the quality (g) of the oil water mixture of absorption organic oil, m2It represents
The quality (g) of oil water mixture before unadsorbed machine oil.
Oil-absorbing process of the hydrophobic porous starch in grease system (referring to Fig. 1 to Fig. 4)
100g deionized waters accurately are weighed, machine oil syringe is injected in water, forms one layer of stable oil on the water surface
Film opens magnetic stirring apparatus, forms oil column in beaker, then the hydrophobic porous starch of preparation is put into beaker, observes it
Oil-absorbing process.
Oil-absorbing process of the Hydrophobic Modified Starch sample in grease system by graph discovery as shown, do not add hydrophobically modified to form sediment
Before powder, machine oil is bubbled through the water column, and Hydrophobic Modified Starch sample is added and after certain time magnetic agitation, hydrophobic porous starch will
The whole absorption of oil on the water surface finish, meanwhile, it is initially dry to become fluffy soft silk floss in powdered hydrophobic porous starch sample
State shows hydrophobic porous starch in grease system while oil suction it can be found that its color is shallower than the color of original machine oil
Part water can be absorbed, and the hydrophobic porous starch sample bubbled through the water column originally can be sunken to beaker bottom, convenient for solving at the later stage
Manage the separating and filtering problem after oily water.
Open oil-contaminated water processing method, which is characterized in that comprise the following steps, containing region prevents oil on the water surface
Dirt continues to spread；The mode contained is to use containment structure, and containment structure includes lower section buoyant foam 1, in lower section buoyant foam 1
Side contains plate 2 comprising top, and plate 2 is contained in top and lower section buoyant foam 1 constitutes containment structure, and containment structure, which surrounds, contains circle 4,
4 inside of circle is contained to contain region 5；
The substance described in this patent is added；Stirring layering；Intercept upper layer substance；Upper layer substance is dried, combustion is used as
Expect spare.
The processing method of closed oily wastewater, which is characterized in that comprise the following steps, collect sewage, be conducted into
In process container；The process container includes oily wastewater import 6, and oily wastewater import is provided with adding mouth 7 on 6 inside, adds
The substance that can be added in mouth 7 described in this patent, the substance that oily wastewater can impact this patent addition is added so that it is impacted
In container；Layering；Intercept upper layer substance, separation lower layer substance；Lower section receiver 9 is the double-deck platy structure, the double-deck platy structure
On respectively contain hole, the mesh of lower section receiver can be adjusted by changing the registration in hole of the double-deck platy structure, when with lifting
Part 10 pulls lower section receiver 9 when move downward, and the mesh of lower section receiver is opened, be then added oily wastewater and
The substance of this patent addition；After sedimentation, the mesh of lower section receiver is relatively closed, can opposite resistance by the floating fraction of top
Every；Upper layer substance is dried, it is spare to be used as fuel.
In a creative way, above each effect is individually present, moreover it is possible to the combination of the above results is completed with a nested structure.It needs
Bright, multiple schemes that this patent provides include the basic scheme of itself, independently of each other, do not restrict mutually, but its
It can be combined with each other in the absence of conflict, reach multiple effects and realize jointly.The base of the present invention has been shown and described above
Present principles, main feature and advantages of the present invention.Those skilled in the art should be recognized that the present invention not by above-described embodiment
Limitation, the above embodiments and description only illustrate the principle of the present invention, is not departing from spirit and scope of the invention
Under the premise of, various changes and improvements may be made to the invention, these changes and improvements are both fallen in claimed range.
Claims (10)
1. hydrophobic porous starch, which is characterized in that be prepared using following steps：
（1）The preparation of porous-starch
Starch dispersion is weighed in the citrate-phosphate disodium hydrogen buffer solution that pH is 5, is made into 23%（Mass fraction）Starch
Complex enzyme is added in milk solution（Alpha-amylase and glucase by volume 1:3 mixing）Afterwards in 50 DEG C of enzymolysis, react
Cheng Hou, reacting 15 min to 3 with 5% salt acid for adjusting pH makes enzyme inactivate, finally with the hydrochloric acid in 3% NaOH and in solution；Reaction
After the completion, it is filtered by vacuum, starch is washed with deionized 2-3 times and is placed in air dry oven at 45 DEG C dry 48 h, crushes
80 mesh sieve is crossed afterwards to get to porous enzymatic starch;
（2）The octenyl succinic acid anhydride of porous-starch（OSA）Esterification
Allocate a concentration of 35%（w/w）Enzymatic starch breast, be placed in 35 DEG C of water-baths, be stirred continuously, adjust the pH of starch milk,
Make it in the range of 8.0-8.5,5% OSA is added dropwise in 1 h（W/w accounts for starch on dry basis quality）, in reaction process
With the pH of 3% NaOH solution control systems；It is after reaction neutral with 5% salt acid for adjusting pH；Multiple alcohol is washed, water
It washes, filter and dries sample;
（3）It is esterified the Al of enzymatic starch3+Crosslinking
The starch sample of above-mentioned esterification enzymolysis is taken to be configured to a concentration of 35%（w/w）Starch milk, adjust reaction system pH be 4,
Quantitative Al is added3+, repeatedly washed after reaction with the pH of 3% NaOH maintenance systems in reaction process, suction filtration is placed on
Dry 24 h, obtain composite modified hydrophobic porous starch in 45 DEG C of baking oven.
2. hydrophobic porous starch as described in claim 1, which is characterized in that also include that the hydrophobic porous starch progress is excellent
The step of selecting, the carry out is preferred, refers to that levels starch is obtained after being detached to Hydrophobic Modified Starch particle, and upper layer is formed sediment
The oil absorbency of powder lower layer starch is more preferable, collects upper layer starch.
3. hydrophobic porous starch as described in claim 1, which is characterized in that the amount that the OSA is added is 5%（W/w accounts for starch
Butt quality）.
4.OSA and cornstarch it is one of arbitrary or a combination thereof preparing hydrophobic porous starch or hydrophobic porous oil suction substance
In purposes.
5. a kind of substance of grease factory cleaning oil tank, which is characterized in that the cleaning substance is：Hydrophobic porous starch, it is hydrophobic
Porous-starch is prepared using step as described in claim 1.
6. a kind of high heat solid fuel, which is characterized in that it is hydrophobic porous starch adsorption chemical industry as described in claim 1
It is prepared after grease.
7. use of the hydrophobic porous starch in preparing the environmentally friendly substance for administering oily waste water treatment as prepared by claim 1
On the way.
8. purposes of the hydrophobic porous starch in the emergency management and rescue that oil reveals in water body as prepared by claim 1.
9. open oil-contaminated water processing method, which is characterized in that comprise the following steps, containing region prevents greasy dirt on the water surface
Continue to spread；The mode contained is to use containment structure, and containment structure includes lower section buoyant foam（1）, lower section buoyant foam（1）
Plate is contained comprising top in top（2）, plate is contained in top（2）With lower section buoyant foam（1）Containment structure is constituted, containment structure surrounds
Contain circle（4）, contain circle（4）Inside is to contain region（5）；
The substance described in this patent is added；Stirring layering；Intercept upper layer substance；Upper layer substance is dried, it is standby to be used as fuel
With.
10. the processing method of closed oily wastewater, which is characterized in that comprise the following steps, collect sewage, be conducted into everywhere
It manages in container；The process container includes oily wastewater import（6）, oily wastewater import（6）Adding mouth is provided on inside
（7）, adding mouth（7）The middle substance that can be added described in this patent, the substance that oily wastewater can impact this patent addition make it
It is impacted in container；Layering；Intercept upper layer substance, separation lower layer substance；Lower section receiver（9）It is double for the double-deck platy structure
Hole is respectively contained on layer platy structure, the net of lower section receiver can be adjusted by changing the registration in hole of the double-deck platy structure
Hole, when with lifting part（10）Pull lower section receiver（9）When moving downward, the mesh of lower section receiver is opened, with
The substance of oily wastewater and this patent addition is added afterwards；After sedimentation, the mesh of lower section receiver is relatively closed, by top
Floating fraction can opposite barrier；Upper layer substance is dried, it is spare to be used as fuel.
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| CN109457004A (en) * | 2018-11-06 | 2019-03-12 | 浙江新和成股份有限公司 | Non-adsorbed starch, non-adsorbed starch aggregate and preparation method, application and nutrient formulation |
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| CN111533816A (en) * | 2020-06-05 | 2020-08-14 | 宁夏大学 | Starch-based fat substitute and method for preparing same |
| CN113041404A (en) * | 2021-03-19 | 2021-06-29 | 北京化工大学 | Preparation method of medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch and product thereof |
| CN113214532A (en) * | 2021-06-25 | 2021-08-06 | 江南大学 | Preparation method of high-load esterified porous starch-based material |
| CN116041623A (en) * | 2022-09-16 | 2023-05-02 | 东莞东美食品有限公司 | Preparation method of porous starch with high oil absorption rate |
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| CN109457004A (en) * | 2018-11-06 | 2019-03-12 | 浙江新和成股份有限公司 | Non-adsorbed starch, non-adsorbed starch aggregate and preparation method, application and nutrient formulation |
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| CN111533816A (en) * | 2020-06-05 | 2020-08-14 | 宁夏大学 | Starch-based fat substitute and method for preparing same |
| CN111533816B (en) * | 2020-06-05 | 2022-03-11 | 宁夏大学 | Starch-based fat substitute and method for preparing same |
| CN113041404A (en) * | 2021-03-19 | 2021-06-29 | 北京化工大学 | Preparation method of medical catheter with ultrasonic imaging capability based on hydrophobic modified porous starch and product thereof |
| CN113214532A (en) * | 2021-06-25 | 2021-08-06 | 江南大学 | Preparation method of high-load esterified porous starch-based material |
| CN116041623A (en) * | 2022-09-16 | 2023-05-02 | 东莞东美食品有限公司 | Preparation method of porous starch with high oil absorption rate |
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| CN108299669B (en) | 2020-08-21 |
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